Preparation method of double-end modified solution polymerized styrene-butadiene rubber

Abstract

The invention provides a preparation method of double-end modified solution polymerized styrene-butadiene rubber. The preparation method comprises the following steps: carrying out anion solution polymerization reaction on aromatic ethylene and conjugated diene in a solvent by taking organic lithium as a reaction initiator and a Lewis base compound as a randomization auxiliary agent; an amino alkoxy silane coupling agent is added for a coupling reaction; and adding a terminator to finish the reaction, adding an antioxidant, and carrying out gas stripping and drying to obtain a solution polymerized styrene-butadiene rubber product. When the styrene-butadiene rubber prepared by the method is applied to a tire tread, the tire can simultaneously obtain excellent characteristics of low rolling resistance and high wet skid resistance, and the styrene-butadiene rubber is excellent in physical and mechanical properties and suitable for green tire tread rubber.

Description

Technical Field

[0001] This invention belongs to the field of rubber synthesis technology, specifically relating to a method for preparing dual-end modified solution-polymerized styrene-butadiene rubber. Background Technology

[0002] The automotive industry is experiencing a surge in demand for energy-efficient and environmentally friendly tires. As a key component affecting vehicle energy efficiency, tire rolling resistance is directly related to fuel consumption and carbon emissions. Studies show that a 10% reduction in rolling resistance can improve vehicle fuel efficiency by 2%-3%. Simultaneously, with the increasing prevalence of new energy vehicles, higher demands are being placed on tires' wet skid resistance (safety) and wear resistance (lifespan). These mutually constraining performance indicators pose significant challenges to rubber material design: reducing rolling resistance requires minimizing energy dissipation (hysteresis loss) caused by the movement of rubber molecular chain ends, while improving wet skid resistance requires increasing the mobility of molecular chain segments at low temperatures. Traditional rubber materials such as natural rubber (NR) or polybutadiene rubber (BR), while possessing low hysteresis loss characteristics, suffer from insufficient wet skid resistance (low tanδ0℃ value), making it difficult to meet the comprehensive requirements of high-performance tires.

[0003] Solution-polymerized styrene-butadiene rubber (SSBR) is an ideal choice for green tire tread compounds due to its designable molecular structure. Anionic solution polymerization allows for precise control of the vinyl content, styrene block sequence, and molecular weight distribution of SSBR. However, traditional SSBR still suffers from two inherent drawbacks: a large number of free ends in the linear molecular chains, leading to significant energy dissipation during interchain slip and increased rolling resistance; and low molecular chain polarity, resulting in weak interaction with reinforcing fillers (carbon black / fumed silica), causing uneven filler dispersion and limiting improvements in mechanical properties.

[0004] To overcome the above-mentioned shortcomings, various modification technologies have been developed, but significant limitations still exist:

[0005] The first method uses special initiators. US5521309 uses hexamethyleneiminoallyl lithium or hexamethyleneiminoxylyllithium as initiators to synthesize solution-polymerized styrene-butadiene rubber containing amino groups. This method also only modifies one end of the molecular chain, resulting in a slight decrease in rolling resistance and generally poor processing performance.

[0006] The second method involves coupling the ends of the active polymer chains with coupling agents to form a star-shaped topology. For example, US4397994A patent uses SnCl4 to couple linear SSBR, reducing the free ends of the molecular chains by 30%-50% and significantly reducing hysteresis loss (tanδ at 60℃ decreases by 15%-20%). However, this technology only modifies the coupling ends of the molecular chains; the initiator ends remain inert alkyl groups (such as butyl), which cannot improve the interaction with the filler, and the rolling resistance remains high.

[0007] In summary, when styrene-butadiene rubber is used in tire treads, the poor dispersion of silica in the rubber leads to high rolling resistance and poor wet skid resistance, which urgently needs to be addressed. Summary of the Invention

[0008] To address the shortcomings of existing technologies, one objective of this invention is to provide a method for preparing dual-end modified solution-polymerized styrene-butadiene rubber (SBR). When the SBR prepared by this method is applied to tire treads, it enables the tire to simultaneously achieve excellent properties such as low rolling resistance and high wet grip, and also exhibits superior physical and mechanical properties, making it suitable for green tire tread compounds.

[0009] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0010] A method for preparing dual-end modified solution-polymerized styrene-butadiene rubber, the method comprising the following steps:

[0011] S1: Anionic solution polymerization of aromatic ethylene and conjugated diene is carried out in a solvent using organolithium as the reaction initiator and Lewis base compound as the randomization auxiliary.

[0012] S2: Add an aminoalkoxysilane coupling agent to carry out a coupling reaction;

[0013] S3: Add a terminator to end the reaction, add an antioxidant, and after air stripping and drying, obtain the solution-polymerized styrene-butadiene rubber product.

[0014] The inventors discovered that nitrogen and silicon atoms bond better with fillers. By using nitrogen-silicon functionalized special initiators and aminoalkoxysilane coupling agents that have better contact with fillers, high-performance styrene-butadiene rubber (SBR) can be obtained. Research showed that using nitrogen-silicon functionalized special initiators significantly reduces the degree of freedom of the active initiation end, effectively controlling the frictional heat generated by small molecules at the chain ends. This greatly improves the compatibility of the SBR with fillers after polymerization, thus significantly reducing rolling resistance. Using aminosiloxane coupling agents, the alkoxy groups can react with the hydroxyl groups on the filler surface, resulting in better dispersion and higher homogenization in the filler. When used together with the aforementioned nitrogen-silicon functionalized special initiators, tire products exhibiting both ultra-low rolling resistance and high anti-skid properties can be obtained.

[0015] In one embodiment of the present invention, the organolithium in S1 is obtained by pre-synthesizing or in-situ in-reactor synthesis of a compound of formula 1 with n-butyllithium:

[0016]

[0017] Among them, R 1 R is methine and / or nitrogen. 2 For methyl and / or phenyl, R 3 For methyl and / or phenyl, R 4 R is methine and / or nitrogen.5 It is one or more of hydrogen, methyl, ethyl, isopropyl, phenyl, and cyclohexyl, where n is a positive integer from 1 to 6; preferably R 1 For nitrogen, R 2 Methyl, R 3 Methyl, R 4 For nitrogen, R 5 Where is hydrogen and n is a positive integer between 2 and 5; preferably, the amount of organic lithium added is 0.5 to 2 mmol / 100g, more preferably 0.6 to 1.5 mmol / 100g.

[0018] In one embodiment of the present invention, the Lewis base compound in S1 is selected from oxygen-containing Lewis bases and / or nitrogen-containing organic bases; preferably, the oxygen-containing Lewis base is tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, bis(tetrahydrofuran)propane, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol dihexyl ether, ethylene glycol dibutyl ether, propylene glycol diethyl ether, 2-ethylfuran, 2-isopropylfuran, 2-butyltetrahydrofuran, 1,4-dioxane, anisole, phenethyl ether, sodium tert-butoxide, potassium tert-butoxide, etc. One or more of sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide are preferred; the nitrogen-containing organic base is one or more of triethylamine, diisopropylethylamine, piperidine, tetramethylpyrrole, dimethylpyrrole, pyridine, 2-methylpyridine, 2,6-dimethylpyridine, methylimidazolium, 4-dimethylaminopyridine, 1,8-diazabicycloundec-7-ene, and tetramethylguanidine; more preferably, the Lewis base compound is bis(tetrahydrofuran)propane; preferably, the molar ratio of the Lewis base compound to the organolithium is 0.8 to 1.8:1.

[0019] In one embodiment of the present invention, the aromatic ethylene in S1 comprises one or more of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, 2-methylaminovinylbenzene, 3-ethylvinylbenzene, 2-vinylnaphthalene, 4-tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-diethylaminostyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, biphenylethylene, and 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene; preferably, the aromatic styrene accounts for 10-50% of the total mass of the monomers, more preferably 15-35%.

[0020] In one embodiment of the present invention, the conjugated olefin in S1 is selected from 1,3-conjugated dienes, preferably 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-cyclohexadiene, 1,3-cyclopentadiene, 3-methyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-heptadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-hexadiene, 5-methyl-1,3-hexadiene, etc. One or more of 3-hexadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 1,3-octadiene, 2-methyl-1,3-heptadiene, 6-methyl-2,4-heptadiene, 1,3-nonadiene, 1,3-decadiene, 7-methyl-3-methylene-1,6-octadiene, farnesene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene; preferably, the conjugated diene accounts for 50-90% of the total mass of the monomers, more preferably 60-80%.

[0021] In one embodiment of the present invention, the solvent in S1 is a hydrocarbon solvent.

[0022] In one embodiment of the present invention, the polymerization temperature in S1 is 0 to 130°C, preferably 50 to 80°C; the polymerization gauge pressure is 0.1 to 0.8 MPa, preferably 0.2 to 0.4 MPa; and the polymerization reaction time is 15 min to 3 h, preferably 30 min to 2 h.

[0023] In one embodiment of the present invention, the alkoxysilane coupling agent described in S2 is preferably (N,N-dimethyl-3-aminopropyl)trimethoxysilane, N,N-diethyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)-N-methylamine, N,N-diethyl-3-triethoxysilylpropyl-1-amine, 3-methylpiperazinyltrimethoxysilane, 4-[3-(trimethoxysilyl)propyl]morpholine, 4-[3-(triethoxysilyl)propylmorpholine, 1-methyl-4-(3-(triethoxysilyl)propyl]morpholine, etc. Piperazine, N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazole, N-[5-(trimethoxysilylpropyl)-2-aza-1-oxopentyl]caprolactam, 1-[3-(triethoxysilyl)propyl]-1H-pyrrole-2,5-dione, propyltriethoxysilane isocyanate, N-aminoethyl-3-aminopropyltriethoxysilane, 3-(azidopropyl)triethoxysilane, 3-isothiocyanopropyltriethoxysilane, 3-(1,3-dimethylbutene)aminopropyltriethoxysilane, (N,N-dimethyl- 3-Aminopropyl)dimethoxymethylsilane, N,N-diethyl-3-aminopropyldimethoxymethylsilane, bis(3-dimethoxymethylsilylpropyl)-N-methylamine, N,N-diethyl-3-dimethoxymethylsilylpropyl-1-amine, 3-methylpiperazinepropyldimethoxymethylsilane, 4-[3-(dimethoxymethyl)propyl]morpholine, 4-[3-(dimethoxymethylsilyl)propylmorpholine, 1-methyl-4-(3-(dimethoxymethylsilyl)propyl)piperazine, N-[3-(dimethoxymethylsilyl)propyl] One or more of the following: -4,5-dihydroimidazole, N-[5-(dimethoxymethylsilylpropyl)-2-aza-1-oxopentyl]caprolactam, 1-[3-(dimethoxymethylsilyl)propyl]-1H-pyrrole-2,5-dione, propyl isocyanate dimethoxymethylsilane, N-aminoethyl-3-aminopropyl dimethoxymethylsilane, 3-(azidopropyl)dimethoxymethylsilane, and 3-isothiocyanopropyl dimethoxymethylsilane; preferably, the molar ratio of the siloxane coupling agent to the organolithium initiator is (0.4-2):1.

[0024] In one embodiment of the present invention, a siloxane coupling agent is added in step S2 after the monomer conversion rate reaches 98% or more.

[0025] In one embodiment of the present invention, the terminator in S3 is a hydroxyl compound, preferably one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, cyclohexanol, ethylene glycol, glycerol, benzyl alcohol, allyl alcohol, isoamyl alcohol, furfuryl alcohol, phenethyl alcohol, xylitol, sorbitol, menthol, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, malic acid, 2,3-dihydroxysuccinic acid, citric acid, benzoic acid, o-hydroxybenzoic acid, phthalic acid, terephthalic acid, and 2-hydroxypropionic acid; preferably, the amount of terminator is 0.2-8% of the total mass of the monomers, more preferably 0.5-5%.

[0026] In one embodiment of the present invention, the antioxidant described in S3 is an organic phenol and / or amine, preferably one or more of p-tert-butylcatechol, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, and N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine; preferably, the amount of antioxidant is 0.5-4% of the total mass of the monomers, more preferably 0.8-2%.

[0027] Another object of the present invention is to provide a dual-end modified solution-polymerized styrene-butadiene rubber.

[0028] A dual-end modified solution-polymerized styrene-butadiene rubber, wherein the rubber is prepared by the above-described preparation method, and the Mooney viscosity ML(1+4) at 100℃ is 65-95; molecular weight and its distribution are: number average molecular weight 150,000-550,000, molecular weight distribution 2.5-3.0; tanδ at 60℃ is 0.052-0.080, tanδ at 0℃ is 0.301-0.500.

[0029] Another object of the present invention is to provide an application of dual-end modified solution-polymerized styrene-butadiene rubber.

[0030] An application of a dual-end modified solution-polymerized styrene-butadiene rubber, wherein the rubber is prepared by the above-described preparation method or is the above-described styrene-butadiene rubber, and the styrene-butadiene rubber is used in a low rolling resistance tire tread compound.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] 1. Using a special initiator functionalized with nitrogen and silicon, compared with other initiators, the rolling resistance of the styrene-butadiene rubber obtained after polymerization is significantly reduced, and the processing performance is further improved.

[0033] 2. Using aminosiloxane coupling agents further improves the dispersibility of fillers. When used together with the above-mentioned special initiators with nitrogen-silicon functionalization, tire products with both low rolling resistance and high anti-skid performance can be obtained. Detailed Implementation

[0034] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0035] Bistetrahydrofuran propane (Annegi, 99%), 2,5-dimethyltetrahydrofuran (Annegi, 98%), anisole (Maclean, 99%), potassium tert-butoxide (Aladdin, 98%), bistetrahydrofuran propane (TCI, 97%), triethylamine (Sinopharm, 99.5%), sodium methoxide (Aladdin, 99%), pyridine (Maclean, 99.5%), ethylene glycol dimethyl ether (Annegi, 99%), 4-dimethylaminopyridine (Aladdin, 99%), 4-dimethylaminopyridine (TCI, 99%), tetrahydrofuran (Sinopharm, 99.5%), 1,4-dioxane (Maclean, 99.5%), 1,8-diazabicycloundec-7-ene (Aladdin, 98%), and methylimidazole (Annegi, 99%). Styrene (Aladdin, 99.5%), 4-methylstyrene (TCI, 98%), 4-ethylstyrene (Maclean, 97%), N,N-dimethylaminomethylstyrene (Annegi, 98%), N,N-dimethylaminomethylstyrene (Bide, 97%), 4-ethylstyrene (Aladdin, 97%), 4-tert-butylstyrene (TCI, 98%), 5-tert-butyl-2-methylstyrene (Annegi, 97%), 2-tert-butylstyrene (Maclean, 96%). 1,3-Butadiene (Linde, 99.9%), 1,3-Pentadiene (TCI, 97%), 1,3-Pentadiene (Maclean, 98%), 3-Methyl-1,3-Pentadiene (Annegi, 95%), 3-Methyl-1,3-Pentadiene (Aladdin, 96%), 4-Methyl-1,3-Pentadiene (Bide, 95%), 6-Methyl-2,4-Heptadiene (TCI, 98%), 1,3-Nonadiene (Annegi, 96%), 2-Methyl-1,3-Hexadiene (Maclean, 97%).(N,N-Dimethyl-3-aminopropyl)trimethoxysilane (Gade, 98%), 4-[3-(trimethoxysilyl)propyl]morpholine (Aladdin, 97%), N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazole (Bailinwei, 95%), 4-[3-(triethoxysilyl)propyl]morpholine (TCI, 97%), N,N-diethyl-3-dimethoxymethylsilylpropyl-1-amine (Annegi, 95%), 1-methyl-4-(3-(dimethoxymethylsilyl)propyl)piperazine (Maclean, 97%), 1-[3-(triethoxysilyl)propyl]-1H-pyridine Pyrrolo-2,5-dione (Bide, 98%), 1-[3-(dimethoxymethylsilyl)propyl]-1H-pyrrolo-2,5-dione (Aladdin, 96%), 3-methylpiperazinepropyldimethoxymethylsilane (Anneji, 95%), N-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole (Bailinwei, 95%), propyltriethoxysilane isocyanate (Gade, 97%), bis(3-dimethoxymethylsilylpropyl)-N-methylamine (TCI, 95%), 3-(azidopropyl)dimethoxymethylsilane (Aladdin, 95%), silicon tetrachloride (Guoyao, 99.5%). Ethanol (Sinopharm, analytical grade AR), methanol (Sinopharm, analytical grade AR), isopropanol (Maclean, 99.7%), ethylene glycol (Aladdin, 99%), formic acid (Annegi, 99%), menthol (TCI, 99%), phthalic acid (Aladdin, 99.5%). 2,6-Di-tert-butyl-p-methylphenol (Aladdin, 99%), p-tert-butylcatechol (Maclean, 99%), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (Annegi, 98%), N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine (TCI, 97%). Butadiene rubber (Sinopec, grade BR9000, Mooney viscosity ML(1+4) 100℃: 45±5, cis-1,4 structure content ≥96%), filler oil (Shell, grade VivaTec 400, aromatic content ≤1.5%, viscosity (40℃) approximately 95cSt), silica (Solvay, grade Zeosil 1165MP, BET specific surface area approximately 160-170m²). 2 / g), carbon black (Cabot, grade N330, DBP absorption value approximately 102 cm⁻¹ ...). 3 / 100g, BET specific surface area is approximately 78m² 2 / g), Si69 coupling agent (Nanjing Shuguang, brand name KH-Si69, active ingredient ≥98%, sulfur content ≥22%), stearic acid (Fengyi Chemical, brand name 1801, iodine value ≤2.0gI2 / 100g, acid value 205-210mg KOH / g), 4-tert-butyl-p-phenol (Aladdin, brand name T801, purity ≥99%, tert-butyl content ≥99.5%), zinc oxide (Guoyao, brand name nano zinc oxide, purity ≥99.7%, average particle size about 30-50nm), tetramethylthiuram disulfide (Maclean, brand name TMTD, purity ≥98%, melting point 148-152℃), sulfur (Guoyao, brand name insoluble sulfur HD OT20, total sulfur content ≥99.5%, thermal stability 120℃×15min ≥75%).

[0036] (Inokai, 98%) (Aladdin, 97%) (Inokai, 98%) (Aladdin, 99%) (Annegi, 99%).

[0037] Preparation Example 1

[0038] Preparation of compound A1 of formula 1:

[0039]

[0040] Initiator precursor synthesis: 0.5 mol of hydrogen-containing double-ended silicone oil was added dropwise at 80 °C, containing 1 mol of allyl piperazine and 0.01 mmol of chloroplatinic acid (Aladdin, 98%).

[0041] Initiator 1 precursor 1 H NMR(500MHz,Chloroform-d)δ2.72(ddd,J=6.8,5.3,2.6Hz,8H),2.59(dt,J=11.3,5.3,3.4,2.6Hz,8H),2.44(t,J=6.8Hz,4 H),1.93(q,J=3.3Hz,2H),1.49(tt,J=8.9,6.8Hz,4H),0.77(t,J=8.9Hz,4H),0.10(s,6H),0.01(d,J=5.1Hz,24H).Chemical Formula:C 24 H 60 N4O4Si5 Exact Mass: 608.3461. Initiator 2 precursor. 1H NMR(500MHz,Chloroform-d)δ2.70(ddd,J=6.8,5.3,2.6Hz,8H),2.58(dt,J=11.3,5.3,3.4,2.6Hz,8H),2.44(t,J=6.8Hz,4 H),1.91(p,J=3.4Hz,2H),1.48(tt,J=8.9,6.8Hz,4H),0.77(t,J=8.9Hz,4H),0.11(s,9H),0.01(d,J=5.1Hz,25H).Chemical Formula:C 26 H 66 N4O5Si6. Exact Mass: 682.3649.

[0042] Preparation of the special initiator: In a low-temperature constant temperature reaction bath at 10℃, the special initiator precursor (0.3 mmol) and 20 mL of cyclohexane were dissolved in a 250 mL round-bottom flask, and an equal amount of n-butyllithium was slowly added to the above solution. The n-butyllithium reacted with the precursor in a 1:1 ratio to generate an equal amount of n-butane and the special initiator. The successful synthesis of the special initiator can be confirmed by monitoring the n-butane in the gas phase.

[0043] Preparation of the compound: Using the above-described dual-end modified styrene-butadiene rubber, the components are compounded according to the formulation shown in Table 1 below to prepare the final compound. The compounding is carried out by the following method: In the primary compounding, raw rubber (a conjugated diene-based polymer), fillers, organosilane coupling agents, filler oils, zinc oxide, stearic acid, carbon black, tert-butyl-p-phenol, anti-aging agents, waxes, and Si69 coupling agents are compounded at 80 rpm using an internal mixer equipped with a temperature controller. For this purpose, the temperature of the mixer is controlled, and a first-stage mixture is obtained at a discharge temperature of 140°C to 150°C. In the second-stage compounding, the first-stage mixture is cooled to room temperature, and then the rubber, sulfur, and vulcanization accelerator tetramethylthiuram disulfide are placed in the mixer, and a second-stage compound is obtained at a discharge temperature of 45°C to 60°C. In the third-stage compounding, the second-stage compound is shaped and vulcanized at 180°C for 100 minutes using a vulcanizing press, thereby producing vulcanized rubber.

[0044]

[0045] The testing method is as follows:

[0046] Mooney viscosity: Tested using GB / T 1232.1 method. A Mooney viscometer (TAIDI YF-8005) was used, based on JIS K6300, at an L rotor, 1 minute preheating time, 4 minutes rotor rotation time, and 100℃. Molecular weight and molecular weight distribution: Tested using an Agilent 1260 Infinity II gel permeation chromatograph, using THF as the mobile phase. Chromatograms were measured using a GPC with three columns packed with polystyrene-based gel. Molecular weights (Mw, Mn) were calculated based on a calibration curve using standard polystyrene, and then the ratio of the lowest molecular weight peak area to the total peak area was calculated.

[0047] The tanδ0℃ value of the rubber compound was measured using a dynamic spectrometer manufactured by Rheometrix Corporation, USA, under conditions of 0.1% dynamic tensile strain, 10Hz frequency, and 0℃. The results are expressed exponentially; a higher value indicates greater and better wet skid resistance. The tanδ60℃ value of the rubber compound was measured using a dynamic spectrometer manufactured by Rheometrix Corporation, USA, under conditions of 1% dynamic tensile strain, 10Hz frequency, and 60℃. The results are expressed exponentially; a higher value indicates lower rolling resistance, and better rolling resistance.

[0048] Physical and mechanical properties: Tested according to GB / T 8656-1998. Tensile strength and tensile stress (300% modulus) at 300% elongation were determined according to ASTM 412 tensile testing method. For this purpose, an Instron 4204 general-purpose testing machine was used, and tensile strength, modulus, and elongation were measured at room temperature with a tensile speed of 50 cm / min. Abrasion was measured using a Lamborn abrasion tester, expressed as abrasion at a slip coefficient of 25%, and at room temperature. A higher index indicates better abrasion resistance.

[0049] In the examples, the special organic lithium was diluted with n-hexane to 0.10 mol / L.

[0050] Example 1

[0051] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After heating the system to 35°C, 6.0mL (0.10M) of special initiator precursor 1 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 75°C to begin the polymerization reaction. The reaction gauge pressure was [not specified]. After polymerization at 0.35 MPa for 40 min, the monomer conversion reached 100%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium of 1:0.4. The coupling reaction ended after 15 min, and 2.0 g of ethanol was added to terminate the reaction. Subsequently, 1.0 g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0052] Example 2

[0053] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After the system was heated to 35°C, 6.0mL (0.10M) of a special initiator precursor 2 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 75°C to start the polymerization reaction, with a reaction gauge pressure of 0.35MPa. After 40 minutes of polymerization, the monomer conversion rate reached 100%. A (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for a coupling reaction. The molar ratio of this agent to active lithium was 1:0.4. The coupling reaction ended after 15 minutes. 2.0g of ethanol was added to terminate the reaction, followed by the addition of 1.0g of... 2,6-Di-tert-butyl-p-methylphenol was stirred for 15 min, then subjected to nitrogen stripping for 5 h and dried to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymer are shown in Table 1.

[0054] Example 3

[0055] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of tetrahydrofuran propane to n-butyllithium was 0.9:1. After heating the system to 35°C, 6.0mL (0.10M) of special initiator precursor 3 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 75°C to begin the polymerization reaction. The reaction gauge pressure was [not specified]. After polymerization at 0.35 MPa for 40 min, the monomer conversion reached 100%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium of 1:0.4. The coupling reaction ended after 15 min, and 2.0 g of ethanol was added to terminate the reaction. Subsequently, 1.0 g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0056] Example 4

[0057] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After heating the system to 35°C, 10.0mL (0.10M) of special initiator precursor 4 and 1.0mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 75°C to begin the polymerization reaction. The reaction gauge pressure was [not specified]. After polymerization at 0.35 MPa for 40 min, the monomer conversion reached 100%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium of 1:0.4. The coupling reaction ended after 15 min, and 2.0 g of ethanol was added to terminate the reaction. Subsequently, 1.0 g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0058] Example 5

[0059] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 1.0:1. After the system was heated to 35°C, 8.0mL (0.10M) of special initiator precursor 1 and 0.8mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin the polymerization reaction. The gauge pressure was 0.24 MPa. After 40 min of polymerization, the monomer conversion rate reached 100%. 4-[3-(trimethoxysilyl)propyl]morpholine coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of 4-[3-(trimethoxysilyl)propyl]morpholine to active lithium of 1:1.4. The coupling reaction ended after 15 min, and 2.0 g of methanol was added to terminate the reaction. Subsequently, 1.0 g of p-tert-butylcatechol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0060] Example 6

[0061] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 1.1:1. After the system was heated to 35°C, 9.0mL (0.10M) of special initiator precursor 1 and 0.9mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 65°C to start the polymerization reaction, with a reaction gauge pressure of 0.34MPa. After 35 minutes of polymerization, the monomer conversion rate reached 100%. N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazolium coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazolium to active lithium was 1:0.8. The coupling reaction ended after 15 minutes. 2.0g of isopropanol was added to terminate the reaction, followed by the addition of 1.0g of [unspecified substance]. N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine was stirred for 15 min, then subjected to nitrogen stripping for 5 h and dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0062] Example 7

[0063] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 10g of styrene, 40g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of 2,5-dimethyltetrahydrofuran to n-butyllithium was 1.2:1. After the system was heated to 35°C, 11.0mL (0.10M) of special initiator precursor 1 and 1.1mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 70°C to start the polymerization reaction, with a reaction gauge pressure of 0.34MPa. After 35 minutes of polymerization, the monomer conversion rate reached 100%. N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazolium coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazolium to active lithium of 1:0.8. The coupling reaction ended after 15 minutes, and 2.0g of isopropanol was added to terminate the reaction, followed by the addition of 1.0g of […]. N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine was stirred for 15 min, then subjected to nitrogen stripping for 5 h and dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0064] Example 8

[0065] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 12g of styrene, 38g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of anisole to n-butyllithium was 1.3:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 1 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 70°C to begin the polymerization reaction, with a reaction gauge pressure of 0.34MPa. After 35 minutes of polymerization, the monomer conversion rate reached 100%. 4-[3-(triethoxysilyl)propylmorpholine coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of 4-[3-(triethoxysilyl)propylmorpholine to active lithium of 1:0.8. The coupling reaction ended after 15 minutes, and 2.0 g of ethylene glycol was added to terminate the reaction. Subsequently, 0.4 g of N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine was added, and the mixture was stirred for 15 minutes. After nitrogen stripping for 5 hours, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0066] Example 9

[0067] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of potassium tert-butoxide to n-butyllithium was 1.4:1. After the system was heated to 35℃, 6.0mL (0.10M) of special initiator precursor 1 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55℃ to start the polymerization reaction, and the reaction gauge pressure was 0.24MPa. After 40min of polymerization, the monomer conversion rate reached 100%. 4-[3-(trimethoxysilyl)propyl]morpholine coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of morpholine to active lithium was 1:1.9. After 15min, the coupling reaction ended, and 2.0g of methanol was added to terminate the reaction. Then, 0.8g of p-tert-butylcatechol was added, and the mixture was stirred for 15min. After nitrogen stripping for 5h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymerized product are shown in Table 1.

[0068] Example 10

[0069] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 1.5:1. After the system was heated to 35°C, 12.0mL (0.10M) of special initiator precursor 1 and 1.2mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin the polymerization reaction. The reaction gauge pressure was... At a pressure of 0.24 MPa, after 40 min of polymerization, the monomer conversion reached 100%. Nitrogen-diethyl-3-dimethoxymethylsilylpropyl-1-amine coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of 1:0.5 to active lithium. The coupling reaction ended after 15 min, and 0.3 g of formic acid was added to terminate the reaction. Subsequently, 1.0 g of p-tert-butylcatechol was added, and after stirring for 15 min, nitrogen stripping was performed for 5 h, followed by drying to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0070] Example 11

[0071] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of triethylamine to n-butyllithium was 1.6:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 1 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin the polymerization reaction, with a reaction gauge pressure of 0.24. After polymerization at MPa for 40 min, the monomer conversion reached 100%. 1-Methyl-4-(3-(dimethoxymethylsilyl)propyl)piperazine coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of 1:0.5 to active lithium. The coupling reaction ended after 15 min, and 0.3 g of menthol was added to terminate the reaction. Subsequently, 1.0 g of p-tert-butylcatechol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0072] Example 12

[0073] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of sodium methoxide to n-butyllithium was 1.7:1. After the system was heated to 35°C, 13.0mL (0.10M) of special initiator precursor 1 and 1.3mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin the polymerization reaction, with a reaction gauge pressure of 0.24M. After 40 min of polymerization, the monomer conversion reached 100%. 1-[3-(triethoxysilyl)propyl]-1H-pyrrole-2,5-dione coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of 1-[3-(triethoxysilyl)propyl]-1H-pyrrole-2,5-dione to active lithium was 1:0.6. The coupling reaction ended after 15 min, and 0.3 g of menthol was added to terminate the reaction. Subsequently, 1.0 g of p-tert-butylcatechol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0074] Example 13

[0075] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of 4-methylstyrene, 35g of 1,3-pentadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of pyridine to n-butyllithium was 1.8:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 2 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin the polymerization reaction, with a reaction gauge pressure of 0.24M. After 40 min of polymerization, the monomer conversion reached 100%. 1-[3-(triethoxysilyl)propyl]-1H-pyrrole-2,5-dione coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of 1-[3-(triethoxysilyl)propyl]-1H-pyrrole-2,5-dione to active lithium was 1:0.6. The coupling reaction ended after 15 min, and 1.0 g of phthalic acid was added to terminate the reaction. Subsequently, 1.0 g of p-tert-butylcatechol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0076] Example 14

[0077] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 16g of 4-ethylstyrene, 34g of 1,3-pentadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of ethylene glycol dimethyl ether to n-butyllithium was 0.9:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 3 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 60°C to begin the polymerization reaction. With a gauge pressure of 0.31 MPa, the monomer conversion rate reached 100% after 100 min of polymerization. 3-methylpiperazinepropyldimethoxymethylsilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of 3-methylpiperazinepropyldimethoxymethylsilane to active lithium of 1:1. The coupling reaction ended after 15 min, and 2.0 g of ethanol was added to terminate the reaction. Subsequently, 2.0 g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0078] Example 15

[0079] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of N,N-dimethylaminomethylstyrene, 35g of 3-methyl-1,3-pentadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of 4-dimethylaminopyridine to n-butyllithium was 0.9:1. After the system was heated to 35°C, 14.0mL (0.10M) of a special initiator precursor 4 and 1.4mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 52°C to start the polymerization reaction, with a reaction gauge pressure of 0.28MPa. After 110 minutes of polymerization, the monomer conversion rate reached 100%. N-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of N-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole to active lithium was 1:1.5. The coupling reaction ended after 15 minutes. 0.8g of ethanol was added to terminate the reaction, followed by the addition of 0.6g of [unspecified substance]. 2,6-Di-tert-butyl-p-methylphenol was stirred for 15 min, then subjected to nitrogen stripping for 5 h and dried to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymer are shown in Table 1.

[0080] Example 16

[0081] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of N,N-dimethylaminomethylstyrene, 35g of 3-methyl-1,3-pentadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of 4-dimethylaminopyridine to n-butyllithium was 0.9:1. After the system was heated to 35°C, 6.0mL (0.10M) of a special initiator precursor 4 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to start the polymerization reaction, with a reaction gauge pressure of 0.30MPa. After 110 minutes of polymerization, the monomer conversion rate reached 100%. N-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of N-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole to active lithium was 1:1.5. The coupling reaction ended after 15 minutes. 0.8g of ethanol was added to terminate the reaction, followed by the addition of 0.6g of [unspecified substance]. 2,6-Di-tert-butyl-p-methylphenol was stirred for 15 min, then subjected to nitrogen stripping for 5 h and dried to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymer are shown in Table 1.

[0082] Example 17

[0083] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of 4-ethylstyrene, 35g of 4-methyl-1,3-pentadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of tetrahydrofuran to n-butyllithium was 0.9:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 4 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin polymerization. The reaction was carried out at a gauge pressure of 0.30 MPa. After 60 min of polymerization, the monomer conversion rate reached 100%. Propyltriethoxysilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of propyltriethoxysilane to active lithium of 1:0.6. The coupling reaction ended after 15 min, and 0.8 g of ethanol was added to terminate the reaction. Subsequently, 0.8 g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 min. After nitrogen stripping for 5 h, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0084] Example 18

[0085] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of 4-tert-butylstyrene, 35g of 6-methyl-2,4-heptadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of 1,4-dioxane to n-butyllithium was 0.9:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 1 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 55°C to begin the polymerization reaction. The reaction pressure was 0.27 MPa. After 60 min of polymerization, the monomer conversion rate reached 100%. Bis(3-dimethoxymethylsilylpropyl)-N-methylamine coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of bis(3-dimethoxymethylsilylpropyl)-N-methylamine to active lithium of 1:0.8. The coupling reaction ended after 15 min, and 1.4 g of ethanol was added to terminate the reaction. Subsequently, 1.0 g of p-tert-butylcatechol was added, and after stirring for 15 min, nitrogen stripping was performed for 5 h, followed by drying to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0086] Example 19

[0087] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 11g of 5-tert-butyl-2-methylstyrene, 39g of 1,3-nonadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of 1,8-diazabicycloundec-7-ene to n-butyllithium was 0.9:1. After the system was heated to 35°C, 15.0mL (0.10M) of special initiator precursor 1 and 1.5mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 50°C. The polymerization reaction started at 5℃ with a reaction gauge pressure of 0.27 MPa. After 80 min of polymerization, the monomer conversion rate reached 100%. 3-(azidopropyl)dimethoxymethylsilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of 3-(azidopropyl)dimethoxymethylsilane to active lithium of 1:0.8. The coupling reaction ended after 15 min, and 1.4 g of ethanol was added to terminate the reaction. Subsequently, 0.9 g of p-tert-butylcatechol was added, and after stirring for 15 min, nitrogen stripping was performed for 5 h, followed by drying to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0088] Example 20

[0089] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 8g of 2-tert-butylstyrene, 40g of 2-methyl-1,3-hexadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of methylimidazolium to n-butyllithium was 0.9:1. After the system was heated to 35°C, 6.0mL (0.10M) of special initiator precursor 1 and 0.6mmol of n-butyllithium were added to the reactor using a syringe. The polymerization temperature was then set to 63°C to begin the polymerization reaction. The reaction pressure was 0.27 MPa. After 70 min of polymerization, the monomer conversion rate reached 99%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction, with a molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium of 1:0.6. The coupling reaction ended after 15 min, and 1.6 g of ethanol was added to terminate the reaction. Subsequently, 0.9 g of p-tert-butylcatechol was added, and after stirring for 15 min, nitrogen stripping was performed for 5 h, followed by drying to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0090] Comparative Example 1

[0091] The only difference from Example 1 is the use of n-butyllithium initiator.

[0092] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After the system was heated to 35℃, 6.0mL (0.10M) of n-butyllithium was added to the reactor using a syringe. The polymerization temperature was then set to 75℃ to start the polymerization reaction, and the reaction gauge pressure was 0.35MPa. After 40 minutes of polymerization, the monomer conversion rate reached 100%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium was 1:0.4. After 15 minutes, the coupling reaction ended, and 2.0g of ethanol was added to terminate the reaction. Then, 1.0g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 minutes. After nitrogen stripping for 5 hours, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymerized product are shown in Table 1.

[0093] Comparative Example 2

[0094] The only difference from Example 2 is the use of sec-butyllithium initiator.

[0095] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After the system was heated to 35℃, 6.0mL (0.10M) sec-butyllithium was added to the reactor using a syringe. The polymerization temperature was then set to 75℃ to start the polymerization reaction, with a reaction gauge pressure of 0.35MPa. After 40min of polymerization, the monomer conversion rate reached 100%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium was 1:0.4. The coupling reaction ended after 15min. 2.0g of ethanol was added to terminate the reaction, followed by the addition of 1.0g of 2,6-di-tert-butyl-p-methylphenol. After stirring for 15min, nitrogen stripping was carried out for 5h, followed by drying to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymerized product are shown in Table 1.

[0096] Comparative Example 3

[0097] The difference from Example 1 is the use of n-butyllithium initiator and silicon tetrachloride coupling agent.

[0098] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After heating the system to 35℃, 6.0mL (0.10M) of n-butyllithium was added to the reactor using a syringe. The polymerization temperature was then set to 75℃ to start the polymerization reaction, with a reaction gauge pressure of 0.35MPa. After 40 minutes of polymerization, the monomer conversion rate reached 100%. Silicon tetrachloride coupling agent was added to the polymerization reactor to initiate a coupling reaction, with a molar ratio of silicon tetrachloride to active lithium of 1:0.4. The coupling reaction ended after 15 minutes, and 2.0g of ethanol was added to terminate the reaction. Then, 1.0g of 2,6-di-tert-butyl-p-methylphenol was added, and the mixture was stirred for 15 minutes. After nitrogen stripping for 5 hours, the mixture was dried to obtain solution-polymerized styrene-butadiene rubber. The basic data and performance data of the copolymer are shown in Table 1.

[0099] Comparative Example 4

[0100] The only difference from Example 1 is the use of piperidinyl lithium initiator.

[0101] The polymerization reaction was carried out in a 1L stainless steel polymerization reactor. Under an argon atmosphere, 15g of styrene, 35g of 1,3-butadiene, and 390g of n-hexane were added sequentially to the reactor. The molar ratio of bis(tetrahydrofuran)propane to n-butyllithium was 0.9:1. After the system was heated to 35℃, 10.0mL (0.10M) piperidinyllithium was added to the reactor using a syringe. The polymerization temperature was then set to 75℃ to start the polymerization reaction, with a reaction gauge pressure of 0.35MPa. After 40min of polymerization, the monomer conversion rate reached 100%. (N,N-dimethyl-3-aminopropyl)trimethoxysilane coupling agent was added to the polymerization reactor for coupling reaction. The molar ratio of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to active lithium was 1:0.4. The coupling reaction ended after 15min. 2.0g of ethanol was added to terminate the reaction, followed by 1.0g of 2,6-di-tert-butyl-p-methylphenol. After stirring for 15min, nitrogen stripping was carried out for 5h, followed by drying to obtain solution-polymerized styrene-butadiene rubber. The basic and performance data of the copolymerized product are shown in Table 1.

[0102] Table 1 Test data for solution-polymerized styrene-butadiene rubber products

[0103]

[0104] Note: Tanδ(0℃) is the loss factor at 0℃. The higher the value, the better the anti-slip properties; Tanδ(60℃) is the loss factor at 60℃. The lower the value, the lower the rolling resistance.

[0105] As can be seen from the results in Table 1, the wet skid resistance and tensile strength of the vulcanized styrene-butadiene rubber were significantly improved, while also ensuring low rolling resistance and low abrasion performance. The reason for this is that the special initiator containing silicon nitrogen groups can not only interact with the groups on the surface of the filler to improve the dispersibility of the filler, but also greatly improve the processing performance of the rubber. The rubber composition of the present invention is suitable for use as a tire tread compound for all seasons.

Claims

1. A method for preparing dual-end modified solution-polymerized styrene-butadiene rubber, characterized in that, The preparation method includes the following steps: S1: Anionic solution polymerization of aromatic ethylene and conjugated diene is carried out in a solvent using organolithium as the reaction initiator and Lewis base compound as the randomization auxiliary. S2: Add an aminoalkoxysilane coupling agent to carry out a coupling reaction; S3: Add a terminator to end the reaction, add an antioxidant, and after air stripping and drying, obtain the solution-polymerized styrene-butadiene rubber product.

2. The preparation method according to claim 1, characterized in that, The organolithium described in S1 is obtained by pre-synthesis or in-situ synthesis of a compound of formula 1 and n-butyllithium: Among them, R 1 R is methine and / or nitrogen. 2 For methyl and / or phenyl, R 3 For methyl and / or phenyl, R 4 R is methine and / or nitrogen. 5 It is one or more of hydrogen, methyl, ethyl, isopropyl, phenyl, and cyclohexyl, where n is a positive integer from 1 to 6; preferably R 1 For nitrogen, R 2 Methyl, R 3 Methyl, R 4 For nitrogen, R 5 For hydrogen, n is a positive integer between 2 and 5; Preferably, the amount of organic lithium added is 0.5–2 mmol / 100g, more preferably 0.6–1.5 mmol / 100g; And / or, the Lewis base compound described in S1 is selected from oxygen-containing Lewis bases and / or nitrogen-containing organic bases; preferably, the oxygen-containing Lewis base is tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, bis(tetrahydrofuran)propane, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol dihexyl ether, ethylene glycol dibutyl ether, propylene glycol diethyl ether, 2-ethylfuran, 2-isopropylfuran, 2-butyltetrahydrofuran, 1,4-dioxane, anisole, or phenethyl ether. One or more of sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; preferably, the nitrogen-containing organic base is one or more of triethylamine, diisopropylethylamine, piperidine, tetramethylpyrrole, dimethylpyrrole, pyridine, 2-methylpyridine, 2,6-dimethylpyridine, methylimidazolium, 4-dimethylaminopyridine, 1,8-diazabicycloundec-7-ene, and tetramethylguanidine; more preferably, the Lewis base compound is bis(tetrahydrofuran)propane; Preferably, the molar ratio of Lewis base compound to organolithium is 0.8 to 1.8:1; And / or, the aromatic vinylbenzene described in S1 comprises one or more of the following: ethylene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, 2-methylaminovinylbenzene, 3-ethylvinylbenzene, 2-vinylnaphthalene, 4-tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-diethylaminostyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, biphenylethylene, and 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene. Preferably, the aromatic styrene accounts for 10-50% of the total mass of the monomers, more preferably 15-35%; And / or, the conjugated olefin in S1 is selected from 1,3-conjugated dienes, preferably 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-cyclohexadiene, 1,3-cyclopentadiene, 3-methyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-heptadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-pentadiene, 1,3-heptadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-... One or more of the following: hexadiene, 5-methyl-1,3-hexadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 1,3-octadiene, 2-methyl-1,3-heptadiene, 6-methyl-2,4-heptadiene, 1,3-nonadiene, 1,3-decadiene, 7-methyl-3-methylene-1,6-octadiene, farnesene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene; Preferably, the conjugated diene accounts for 50-90% of the total mass of the monomers, more preferably 60-80%; And / or, the solvent in S1 is a hydrocarbon solvent; And / or, the polymerization temperature in S1 is 0 to 130°C, preferably 50 to 80°C; the polymerization reaction gauge pressure is 0.1 to 0.8 MPa, preferably 0.2 to 0.4 MPa; and the polymerization reaction time is 15 min to 3 h, preferably 30 min to 2 h.

3. The preparation method according to claim 1 or 2, characterized in that, The alkoxysilane coupling agent described in S2 is preferably (N,N-dimethyl-3-aminopropyl)trimethoxysilane, N,N-diethyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)-N-methylamine, N,N-diethyl-3-triethoxysilylpropyl-1-amine, 3-methylpiperazinyltrimethoxysilane, 4-[3-(trimethoxysilyl)propyl]morpholine, 4-[3-(triethoxysilyl)propylmorpholine, 1-methyl-4-(3-(triethoxysilyl)propyl) Piperazine, N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazole, N-[5-(trimethoxysilylpropyl)-2-aza-1-oxopentyl]caprolactam, 1-[3-(triethoxysilyl)propyl]-1H-pyrrole-2,5-dione, propyltriethoxysilane isocyanate, N-aminoethyl-3-aminopropyltriethoxysilane, 3-(azidopropyl)triethoxysilane, 3-isothiocyanopropyltriethoxysilane, 3-(1,3-dimethylbutene)aminopropyltriethoxysilane (N,N-Dimethyl-3-aminopropyl)dimethoxymethylsilane, N,N-Diethyl-3-aminopropyldimethoxymethylsilane, bis(3-dimethoxymethylsilylpropyl)-N-methylamine, N,N-diethyl-3-dimethoxymethylsilylpropyl-1-amine, 3-methylpiperazinylpropyldimethoxymethylsilane, 4-[3-(dimethoxymethyl)propyl]morpholine, 4-[3-(dimethoxymethylsilyl)propylmorpholine, 1-methyl-4-(3-(dimethoxymethylsilyl)propyl) Piperazine, N-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole, N-[5-(dimethoxymethylsilylpropyl)-2-aza-1-oxopentyl]caprolactam, 1-[3-(dimethoxymethylsilyl)propyl]-1H-pyrrole-2,5-dione, propylisocyanate dimethoxymethylsilane, N-aminoethyl-3-aminopropyldimethoxymethylsilane, 3-(azidopropyl)dimethoxymethylsilane, and 3-isothiocyanopropyldimethoxymethylsilane are among one or more of these. Preferably, the molar ratio of the siloxane coupling agent to the organolithium initiator is (0.4-2):1; And / or, in S2, a siloxane coupling agent is added after the monomer conversion rate reaches 98% or higher.

4. The preparation method according to any one of claims 1-3, characterized in that, The terminator described in S3 is a hydroxyl compound, preferably one or more of the following: water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, cyclohexanol, ethylene glycol, glycerol, benzyl alcohol, allyl alcohol, isoamyl alcohol, furfuryl alcohol, phenethyl alcohol, xylitol, sorbitol, menthol, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, malic acid, 2,3-dihydroxysuccinic acid, citric acid, benzoic acid, o-hydroxybenzoic acid, phthalic acid, terephthalic acid, and 2-hydroxypropionic acid. Preferably, the amount of the terminator is 0.2-8% of the total mass of the monomers, more preferably 0.5-5%; And / or, the antioxidant described in S3 is an organic phenol and / or amine, preferably one or more of p-tert-butylcatechol, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, and N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine; Preferably, the amount of antioxidant used is 0.5-4% of the total mass of the monomers, and more preferably 0.8-2%.

5. A dual-end modified solution-polymerized styrene-butadiene rubber, wherein the rubber is prepared by the preparation method according to any one of claims 1-4, characterized in that, The Mooney viscosity (ML(1+4)) of the polystyrene-butadiene rubber at 100℃ is 65-95; its molecular weight and distribution are: number average molecular weight 150,000-550,000, molecular weight distribution 2.5-3.0; tanδ at 60℃ is... 0.052-0.080, tan δ0℃: 0.301-0.

500.

6. An application of a dual-end modified solution-polymerized styrene-butadiene rubber, wherein the rubber is prepared by any one of the preparation methods of claims 1-4, or is the styrene-butadiene rubber of claim 5, wherein the styrene-butadiene rubber is used in a low rolling resistance tire tread compound.

Images